Process for rendering fibrous material water-repellent



United States Patent PROCESS FOR RENDERING FIBROUS MATERIAL WATER-REPELLENT Ludwig Orthner and Martin Renter, Frankfurt am Main,

Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Hochst, Germany, a company of Germany a No Drawing. Application October 15, 1953,

Serial No. 386,392 Claims priority, application Germany October 18, 1952 13 Claims. (Cl. 117-1355) In our co-pending U. S. patent application 1 Serial No. 384,528 there is described a process for the preparation of zirconium compounds by reacting zirconium alcoholates with carboxylic and sulfinic acids.

The present invention relates to a process for rendering fibrous material water-repellent by means of the compounds prepared according to the process described in the above-identified U. S. patent application.

It is known to make fibrous material water-repellent by means of aqueous dispersions of zirconium compounds and paraifin. In many cases, however, the process known from the art involves considerable drawbacks, for

instance when impregnating loosely woven fabrics or ready-made clothing, because of the substantial deformation which the materials suffer in the impregnating bath or during the drying process.

Now, we have found that a good hydrophobic effect and a good capacity for repelling water in the form of droplets are obtained, without reducing the permeability to air, by treating fibrous material with solutions in organic solvents, of zirconium alcoholate and/ or mixtures of zirconium and aluminum alcoholate per se and/or in combination with carboxylic or sulfinic acids, or of the reaction products of carboxylic acids or sulfinic acids with zirconium alcoholate, and/ or with mixtures of zirconium and aluminum alcoholate and/or in combination with hydrophobic, organic compounds of high molecular weight, and subsequently drying the treated fabrics, if necessary, at an elevated temperature in the presence or absence of moisture.

The process may also be carried out in the presence of volatile organic substances capable of forming complex compounds.

The process is advantageously carried out by treating and subsequently drying fibrous material, for instance yarn or fabrics, with solutions in organic solvents, of zirconium alcoholates and carboxylic and/ or sulfinic acids which contain the components in a molar proportion of between 1:0.2 to about 4, advantageously in a proportion of between 1:05 to 2, or with solutions of the reaction products of zirconium alcoholate and carboxylic and/or sulfinic acids, obtainable according to the process of U. S. patent application Serial No. 384,528, if desired, with the addition of hydrophobic, organic compounds of high molecular Weight and/or volatile substances capable of forming complex compoundswhich serve to stabilize the zirconium alcoholates and/ or the carboxylic acid zirconium alcoholates against decomposition by moisture. The-zirconium alcoholates may partially be replaced by aluminum alcoholate. The treatment of the fibrous material with the said solutions may be carried through at an'ordinary or. at an elevated temperature. It may be of advantage to subject the thus treated and dried material to an elevated temperature, preferably of 80 C. to 200 C, if desired in the presence of moisture.

1 (Fw. 820/a) filed in our names on October d, 1953, entitle d "ice As zirconium and/or aluminum alcoholates there come into consideration, for instance, those derived from aliphatic alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, amyl alcohol, octyl alcohol and the like.

As carboxylic acids there are suitably used lower aliphatic carboxylic acids, such as formic acid, acetic acid, propionic acid; cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid; aromatic carboxylic acids such as benzoic acid, ortho-, metaor para-chlorobenzoic acid, naphthoic acid. As sulfinic acids there may be mentioned for example: aliphatic sulfinic acids such as ethane sulfinic acid, butane sulfinic acid, furthermore cyclohexane sulfinic acid, benzene sulfinic acid, and naphthene sulfinic acid. .There are especially suitable higher aliphatic and cycloaliphatic carboxylic and sulfinic acids, such as, for instance, oleic acid,'lauric acid, palmitic acid, stearic acid, fatty acids obtained by oxidation as well as mixtures thereof, naphthene acid, resinic acid, montanic acid, fatty acid of sperm oil and sulfinic acids, obtainable in known manner from the sulfochlorination products of fossil and synthetic diesel oil and the like.

As hydrophobic, organic compounds of high molecular Weight there are suitable for instance, solid to semi-solid paraffin hydrocarbons, natural or synthetic waxes, thickly oily to solid polychlorinated hydrocarbons of high molec ular Weight which may be used per se or in admixture with each other.

As solid to semi-solid paraflin hydrocarbons there are suitable for instance, the various forms of solid parafiin for example, 'those having a solidification point of 52? C.54 C., synthetic parafiin hydrocarbons of high molecular weight or mixtures thereof, and also ceresine. Mixtures of solid parafiins with other parafiin hydrocarbons of high molecular weight may also be used, for instance paraffin slack wax.

As natural or synthetic waxes there may be mentioned for instance: carnauba wax, candelilla wax, esters of montanic acids with aliphatic polyhydric alcohols, esters of higher fatty acids with higher fatty alcohols. By the use or addition of waxes the fastness to rubbing of the impregnation is generally improved and the fabric is considerably less susceptible to soiling.

As polychlorinated hydrocarbons of high molecular Weight there are used for instance: the chlorination products of fossil or synthetic aliphatic hydrocarbon oils boiling between about 200 C. and about 400 C., or of fossil or synthetic solid parafiin hydrocarbons solidifying between about 50 C. and about 100 C., or of fossil or synthetic semi-solid parafiin slack waxes, as well as'chlorination products of aromatic hydrocarbons such as naphthalene. The chlorine content of the compounds may vary Within wide limits and may amount up to percent, depending on the purpose for which the finished fabric is to be used.. V I

. When highly chlorinated hydrocarbons are used in the absence of substantial quantities of paraflins or waxes (it being of advantage in this case to use as additional impregnating component reaction products of 1 mol of zirconium alcoholate with less than 0.8 mol of carboxylic acid) vthere are obtained impregnated fabrics having remarkable flame-proof properties in addition to the waterrepellent properties.

As volatile, organic substances capable of forming complex compounds there may be used for instance, compounds containing a weakly acid group, for instance, aliphatic hydroxy-carboxylic esters such as tartaric acid diethyl ester or oximes such as acetone oxime or acetaldehyde oxime;- compounds containing agroup capable of desmotropic rearrangement into the aci-form, such as acetylacetone, acetoacetic ester, malonic acid dinitrile,

nitromethane, nitropropane and the like; compounds containing a reactive methylene group such as, for instance, malonic acid ester; hydroxy-oxo compounds such as butyroin; and aliphatic nitriles such as acetonitrile.

As organic solvents there come into consideration for instance low boiling hydrocarbon or chlorinated hydrocarbons such as benzine, benzene, carbontetrachloride, trichlorethylene, perchlorethylene or mixtures thereof.

The process of the present invention may be used for imparting water-repellent properties to vegetable, animal or synthetic fibrous material such as cotton, linen, viscose fibers, cuprammonium rayon, wool, silk, casein fibers, cellulose acetate fibers, polyamide fibers, polyacrylonitrile fibers, polyester fibers, or mixtures thereof. The fibrous material may be treated before or after it has been worked up.

Very good effects are obtained even when dilute solutions are used. In general it is of advantage to use solutions of 1-10 percent strength. The solutions may be prepared by dissolving the components separately and then mixing the solutions together. When a solution of zirconium alcoholate and a solution of carboxylic acid and/or sulfinic acid are mixed together, the reaction with formation of carboxylic acid, and/or sulfinic acid zirconium alcoholates occurs even in the cold and is completed during the heat treatment to which the fibers are usually subjected.

The components may also be dissolved together. Alternatively, there may be prepared by mixing or fusing together the hydrophobic, organic compounds of high molecular weight and the carboxylic and/or sulfinic acid zirconium alcoholates, a preparation which is dissolved in an organic solvent when required for use. When the fibrous material has been treated with the impregnating liquid the excess of the liquid is removed by drawing oif, squeezing or the like and the fabric is then dried. When garments are to be impregnated, the impregnation process is advantageously carried out in the machines customarily used for dry-cleaning, and the excess of the impregnating liquid is then drawn otf. The impregnated fabric is then centrifuged in the machine and most of the solvent is distilled oif at a raised temperature. The residual solvent is removed by blowing in hot air which, if necessary, may have a certain content of moisture. In order to improve the water-repellent eifect, the dry goods may be subjected in the usual manner to a heat treatment in drying cabinets and/or by ironing or hot pressing. This heat treatment is advantageously carried out in the presence of steam.

The impregnating liquid which has been drawn or squeezed off may be used again, after strengthening it with the agent imparting the water-repellent properties.

For the impregnating process the fabric is, in general, introduced in an air-dry condition. But it is also possible to reduce the normal moisture content of the fibrous material by drying it before it is impregnated.

The process of the present invention may be combined with other finishing processes, preferably with those which are carried out in an organic solvent, for instance, with a process for rendering fabrics mothproof or with a final finish with a thermoplastic which is soluble in organic solvents, such as polyvinyl acetate or polyacrylic acid esters.

The process of this invention is especially suitable for impregnating outer garments immediately after a dry cleaning process.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto.

Example 1 Air-dry pop n jack s of c ton ar impregnated f r -20 minutes at 60 C., in a Washing machine s itabl for dry-cleaning, at a g0ods-to-liquor-,ratio of 1:10, with a solution containing, per liter of carbon tetrachloride,

10 grams of the condensation product of zirconium ethylate and stearic acid, obtained by the reaction of 1 mol of zirconium ethylate with 1 mol of commercial stearic acid (solidification point 52 C., molecular weight 275) and 10 grams of parafiin (solidification point 52 C.) stabilized against decomposition by atmospheric moisture by the addition of 1 gram of acetonylacetone. The liquor is then discharged, the fabric is centrifuged and the solvent is distilled ofi at a raised temperature. The fabric is then dried for 15 minutes at C. by means of air having a relative humidity of 30 percent and is then finished by ironing. By this treatment an excellent water droplet repellent effect and very good results in the trough test are obtained.

Instead of the condensation product of zirconium ethylate and stearic acid, the oleic zirconium ethylate or a mixture of 5 grams of stearic zirconium ethylate and 5 grams of stearic aluminum ethylate can be used just as well.

Example 2 Air-dry delustred crepe of regenerated cellulose is passed in a padding machine at 50 C. through a solution containing, per liter of carbon tetrachloride, 15 grams of the condensation product of zirconium ethylate and stearic acid, obtained by the reaction of 1 mol of zirconium ethylate with 2 mols of commercial stearic acid, and stabilized against decomposition by atmospheric moisture by the addition of 1 gram of acetonylacetone. The liquor is squeezed off and the fabric is dried at a raised temperature by means of air. The fabric is then heated for 30 minutes at 80 C. in a drying cabinet, by means of air having approximately a relative humidity of 20 percent. By this treatment good Water-repellent properties are imparted to the fabric. When proceeding in the same manner but starting from a solution which contains, per liter of carbon tetrachloride, 1.0 grams of zirconium ethylate and 20 grams of parafiin which is stabilized against decomposition by atmospheric moisture by the addition of 1 gram of acetonylacetone, an equally good result is obtained.

Example 3 A gabardine fabric of wool is impregnated for v 10 minutes at about 20 C. at a goods-to-liquor-ratio of 1:12 with a solution of the condensation product of zirconium isopropylate, stearic acid and acetic acid prepared as described below. The liquor is then squeezed off until the increase in weight is about percent and the fabric is dried at about C. by means of hot air. By this treatment an excellent water droplet repellent effect and very good results in the trough test as well as remarkable flame-proof properties are obtained.

The impregnation bath is obtained by dissolving, per liter of perchlorethylene, 10 grams of zirconium isopropylate, 8 grams of stearic acid (solidification point 52 C., molecular weight 270), 2 grams of glacial acetic acid, 10 grams of paraffin, and 20 grams of chlorinated paraflin (chlorine content 40 percent). The glacial acetic acid may partly or wholly be replaced by the equivalent quantity of formic acid.

When proceeding in the same manner, a good waterrepellent impregnation of fabrics of polyamide and polyester fibers is likewise obtained.

Example 4 By the method described in Example 2 a poplin fabric of cotton is impregnated at about 20 C. with a solution in test benzine of dodecylsulfinic zirconium isopropylate and parafiin, and the material is finished. By this treatment good water-repellent properties are imparted to the fabric.

The impregnating bath is obtained by dissolving, per liter of test benzine, 20 grams of the condensation product of zirconium isopropylate and 0.8 mol of dodecylsulfinic acid (compare U. S. patent application Serial No.

384,528) and 20 grams of'parafiin (solidification point 54 C.). The solution thus obtained may be stabilized at ordinary-temperature against decomposition by atmospheric moisture by adding grams of acetoacetic acid ester. When proceeding in the same manner but using instead of dodecylsulfinic acid the equivalent quantity of lauric or benzoic acid, equally good results are obtained. 7

Example 5 Rain-wear of cotton, wool or polyamide fibers or mixed fabrics of these fibers are first dry-cleaned in the usual manner by means of aliphatic hydrocarbons or chlorin-' ated hydrocarbons. When the dry-cleaning is complete, the fabric is impregnated at about 20 C. according to the method described in Example 1 with a solution of the condensation product of zirconium isopropylate, stearic acid and acetic aoid,-paraffin and test benzine, and

the material is finished. In this manner good water repellent properties are imparted to the fabric.

The impregnating bath is obtained by dissolving, per liter of test benzine, 20 grams of the condensation product of zirconium isopropylate, 2 mols of stearic acid and 2 mols of glacial acetic acid as well as grams of parafiin and 10 grams of paraflin slack wax.

When proceeding in the same manner but using instead of 2 mols of stearic acid 1 mol of palmitic acid and 1 mol of castor oil fatty acid equally good results are obtained.

Example 6 Tent cloth fabrics of cotton are passed at 60 C. in a padding machine through a solution containing, per liter of perchlorethylene or test benzine, 50 grams of the pasty waterproofing agent prepared as described below. The liquid is squeezed off until the increase in weight is about 100 percent and the fabric is then dried at about 110 C. by means of hot air.

In this manner good water-repellent properties are imparted to the fabric.

The pasty waterproofing agent is obtained by reacting at 100 C. 190 kg. of zirconium isopropylate in 800 kg. of perchlorethylene, while stirring, with 68 kg. of stearic acid (solidification point 52 0., molecular weight 270) until a clear solution of stcaric zirconium isopropylate has been obtained to which 430 kg. of parafiin have been molten. The solution solidifies, on cooling, to a pasty mass which is soluble in perchlorethylene and test benzine.

When using the equivalent quantity of zirconium butylate instead of zirconium isopropylate equally good results are obtained.

Example 7 A poplin fabric of cotton is passed at about 20 C. in a padding machine through a solution in perchlorethylene of a lardy impregnating agent of stabilized zirconium isopropylate and paraffin. The liquor is then squeezed OE and the fabric is dried at about 110 C. in a drying cabinet by means of air. By this treatment very good water-repellent properties are imparted to the fabric.

The impregnating bath is obtained by dissolving, in 1400 kg. of perchlorethylene, 327 kg. of zirconium tetraisopropylate, reacting the solution at 60 C. with 260 kg. of ethyl acetoacetate and adding thereto, while stirring, 860 kg. of paraflin (solidification point 54 C.). The mixture thus obtained solidifying to a lardy mass is dissolved in 20 times its volume of perchlorethylene.

When proceeding in the same manner but using instead of zirconium tetra-isopropylate the equivalent quantity of a partially hydrolized zirconium isopropylate having the approximate analytic composition Z1'2(OC3H'I)6O, obtainable according to Bradley, Journal of the Chemical Society, London 1952, page 2034, by reacting ammonia gas and isopropanol containing a little water (2 percent water) with the pyridine complex of the zirconium oxychloride, or by reacting zirconium tetra-isopropylate with 0.5 mol of water in a 1% solution of isopropanol according to the method described by G. Winter (Canadian Paint and Varnish Magazine, volume 25 (1951) pages 12-19) for the preparation of titanium alcoholate, an equally good result is obtained- When using in'the preparation of the lardy impregnating agent, in addition to the compounds specified above, 135 kg. of stearic acid an improved fastness to washing of the impregnated fabric is obtained.

Example 8 Rain-Wear of cotton, wool, polyamide or polyester fibers or mixed fabrics of thesefibers is first dry-cleaned in the usual manner by means of aliphatic hydrocarbons or chlorinated hydrocarbons. When the drycleaningis complete, the fabric is impregnated as described in Example 1 at about 20 C. with a solution in test benzine of the condensation product of zirconium isopropylate and benzoic acid, and the material is finished. By this treatment very good water-repellent properties are imparted to the fabric.

The impregnating bath is obtained by'dissolving, per liter of test benzine, 25 grams of the condensation product of 1 mol of zirconium tetra-isopropylate, 1 mol of benzoic acid and, advantageously, 10 grams of paraffin (solidification point' 60 C.). In order to reduce the flammability of the fabrics there may be added 10 grams of chlorinated paraflin (chlorine content 40 percent) to the impregnating bath.

When proceeding in the same manner but using instead of the zirconium tetra-isopropylate the equivalent quantity of a polymeric zirconium isopropylate, obtainable according to the method described by G. Winter (Canadian Paint and Varnish Magazine, volume 25 (1951) pages 12-19) for the preparation of titanium alcoholate by reacting zirconium tetra-isopropylate with 1 mol of water in a 1% solution of isopropanol, equally good results are obtained.

Instead of 1 mol of benzoic acid 0.5 mol of lauric acid or 0.7 mol of dodecylsulfinic acid or 0.3 mol of oleic acid, added by degrees, as well as 0.3 mol of formic acid may also be used for the reaction with zirconium tetra-isopropylate or polymeric zirconium isopropylate. In order to stabilize the impregnating bath against decomposition by atmospheric moisture there may be added, per mol of zirconium alcoholate, 1 mol of acetoacetic ester or acetylacetone.

Example 9 Umbrella silk of viscose rayon or acetate rayon is impregnated according to the method described in Example 7, in a padding machine with a solution in perchlorethylene of a lardy impregnating agent of stabilized polymeric zirconium isopropylate and the material is finished; By this treatment excellent water-repellent properties are imparted to the umbrella silk.

The impregnating bath is obtained by dissolving, per 1000 kg. of perchlorethylene, 210 kg. of polymeric zirconium isopropylate, prepared according to the method described in Example 8, reacting the solution obtained at 60 C. with 260 kg. of ethyl acetoacetate and adding thereto, while stirring, 1000 kg. of paraffin (solidification point 65 C.), and finally dissolving the mixture thus obtained solidifying to a lardy mass in times its weight of perchlorethylene.

We claim:

1. The process of imparting hydrophobic properties to fibrous material which comprises treating the material with a solution in an organic solvent of a mixture of zirconium alcoholate and an organic acid selected from the group consisting of carboxylic and sulfinic acids.

2. The process according to claim 1, wherein said mixture further contains a hydrophobic organic compound of high molecular weight.

3. The process according to claim 1, wherein said zirconium alcoholate is stabilized by means of a volatile organic compound capable of forming complexes therewith.

4. The process according to claim 1, wherein said zirconium alcoholate is stabilized by means of a volatile organic compound containing a reactive group capable of desmotropic conversion into the aci-form.

5. The process according to claim 1, wherein the fibrous material is subsequently heated at an elevated temperature of about 80 C.

6. The process according to claim 1, wherein the fibrous material is aftertreated at a temperature of about 80 C. in the presence of moisture.

7. The process of imparting hydrophobic properties to fibrous material which comprises treating the material with a solution in an organic solvent of a mixture of zirconium alcoholate and an organic carboxylic acid.

8. The process of imparting hydrophobic properties to fibrous material which comprises treating the material with a solution in an organic solvent of a mixture of zirconium alcoholate and an organic sulfinic acid.

9. The process according to claim 7, wherein said solution further contains aluminum alcoholate.

10. The process according to claim 8, wherein said solution further contains aluminum alcoholate.

11. The fibrous material produced in accordance with the process of claim 1.

12. The process according to claim 1, wherein said mixture further contains a hydrophobic organic compound of high molecular weight, and wherein said zirconium alcoholate is stabilized by means of .a volatile organic compound capable of forming complexes therewith.

13,. The process according :to claim 12, wherein zirconium alcoholate and the organic acid are present in said solution as a reaction product with each other.

References Cited in the file of this patent UNITED STATES PATENTS 

1. THE PROCESS OF IMPARTING HYDROPHOBIC PROPERTIES TO FIBROUS MATERIAL WHICH COMPRISES TREATING THE MATERIAL WITH A SOLUTION IN AN ORGANIC SOLVENT OF A MIXTURE OF ZIRCONIUM ALCOHOLATE AND AN ORGANIC ACID SELECTED FROM THE GROUP CONSISTING OF CARBOXYLIC AND SULFINIC ACIDS. 